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•THE OHIO STATE UNIVERSITY RESEARCH FOUNDATION

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RF Project 69I• Report No. 32

.To:' DEPARHviENT OF THE NAVY •Office of Naval Research' Contract No. Nonr ^t12) ARPA Order No. 23-61; Task 1, Item ^i-

On: ■ STRUCTURAL AND THERMODYNAMIC PROPERTIES OF • POLYATOMIC MOLECULES AT ELEVATED TEMPERATURES

■For the period:

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1 April 1964 - 3Ö June ly64

Submitted "by: David vJhite Department of Chemistry

Date: 30 September l^Sh

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NOTICE: When govemment or other drawings!, speci- fications or other data are used for any purpose other than in connection with a, definitely related government procurement operation, the U. S. Govemment thereby .incurs no responsihility, nor any o'bligation whatsoever; and the fact that the Govern- ment may have formulated, furnished, or in any way supplied the said drawings, specifications, or other data is not to he regarded by implication or other- wise-as in any manner licensing "th© holder or any* other person or corporation, or conveying any rights or permission to manufacture, use or sell any patented invention that may in afiy way be related thereto. o

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STRUCTURAL Mü) THERkODYNAMC PROPERTIES OF POLYATOMIC MOLLCULES AT ELEVATED TEMPERATURES

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The infrared absorption spectra of üiagnesium fluoride and magnesium chloride isolated in solid argon and krypton matrices have been investigated in the region 2UO zo kOOO cm"^. The highest frequency bands for the molecule MgPo are observed at Ökj, 833, and ö23 cm~l in solid krypton. These can be assigned to vj of Mg^P^, Mg^PF^^ and ^^p^. The magnitude of the isotopic shifts suggests a linear or slightly bent molecular configuration. There is some experimental evidence for the bent configuration, namely^ a band in the vicinity of 7^ cm"l which maybe the symmetric stretcn. However it is not clear at the time whether this band can be assigned to the molecular species MgF^. The lowest frequency band observed in the infrared spectrum of * matrix-isolated MgF^ occurs at 2k2 cm"! in solid krypton. It can be assigned to the bending mode, v^. Regardless of whether MgF^ is linear or slightly bent, the new frequency assignment yields thermal functions in good agreement with experiments.

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In matrix-isolated MgClp only one band has been observed which can pos- itively be assigned to this molecule. It occurs at 5^9 un'l in solid krypton. This band is probably the asymmetric stretch, v*. The bending to frequency for tl^e molecule, v^, is estirnkted to fall in the region 150-ldO cm-1 by analogy with MgF^. Thermal functions calculated *from such an assignment, 'assuming a linear configuration are in good agreement with experiments. The infrared studies viM be extended to lower frequencie when the new Pekin- Elmer Model JOl spectrometer is delivered.

$ The above infrared absorption studies were presented and discussed at the Symposium on Molecular Spectroscopy and Structure held in Columbus in June. «

Some preliminary matrix-isolation studies of the isotopic species BH^NHx," BDxNDj, were initiated during the quarter. Investigation of phe infrared absbrption spectra of matrix-isolated CaP2 and CaCl^ were also started this quarter.

Some progress has been made in the interpretation of the fine structure observed in the infrared spectra of matriS-isolated hydrogen halides. A model whici» takes into consideration nearest neighbor interactions between the '"trapped species and the surrounding rare gas atoms has been developed which nearly quantitatively accounts for the observations.

Investigator ^\; J^'r ^\ v^ /-Vyy'V- Date / c?//■+/(' V

v\ CM/-* (\ jsj V , VL Supervisor t V VA/v VA .^ v\ v x-^- Date /r//^/£ 9 ^ f ^.

For the Ohio State University Research Foundation

Executive Director /CA-ZCX^» Q ^^^^^^^^^Date /mc// ^/V ^

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